Treatment of hydrocarbon oils



Patented May 7, 1935 v s I 1. v 2,000,411"

TREATMENT OF HYDBOOARBON- Jaoque 0. Morrell and Gustav Egloih, Chicago,

11]., assignors to Universal Oil Products Company, Chicago, 111., a corporation of- South Dakota i No ApplicatlonDecember 1 931, I

. SerialNo.583,91 6 i 401mm. (eras-9y h This invention relates to the treatment'of hy-' is preferred to pre'f'erablyof the aromatic drocarbon oils and refers more particularly to series such as .chlorine derivatives of benzol, the treatment of low boiling distillates produced toluol; xylol, ;etc.,- for their corresponding sulin the cracking of heavier higher-boiling frac--- phonic or sulphuric acids. l'he reaction of such 6 tions. I derivatives with sodamide (NaNHz) results in More specifically, the invention has referencegeneraliinrsthe eombinationjof the sodium with to a process for treating hydrocarbon mixtures the ;hydr0gen;-,substitutin8 8 9 n hy V undergoing decomposition and conversion r'eac carbon.and thexsi ibstitution of the amino'or NH: tions orthe lower boiling vaporous products 'ofgroup'thiereintdprpduoe orr sp amine 10' these reactions to produce substantial amounts dl'l eigenerahreaction may be typified by. the iol-' 10 of compounds which add materially to the anti living equation: J i u 1 v Y 511120: value of the gasoline produced-from: F 1:;- c +Nam=m +Nac1 s W e the crackin p o e as ip s nt-s'en- .:which Rfrepresents any mono valent hydro erally pra i ed in the petroleum lnduetryvtends arbo'n radicah'eitherof the .alkyl or and groups. 15 to the production of gasolines having vanti-knock :sjmflafly th chlqrine atom in the above equa-- characteristicssuperior to those possessed by' cor em may be substituted by the sulphonic or sulresponding gasoline fractions produced by the 'm groups, t the equations straight run distillation of .crude petroleums,'it i i may frequently happen that the production of a H U 2O cracked gasolineof a knock rating rendering it e I +1n saleable as a premium motor fuel may entail the RSO5H+NNH1=RNH2+NBHSO2 use of relatively severe cracking conditions with v v p I attendant increased losses in fixed gases'and, i-Sodamide is a compound well known inthe coke and a decrease in the overall yield of the arts and is used extensively in the manufacture 25 desired product. In-the majority of cases for of: dyes and in other chemical processes. It is any given stock charged to the cracking process, usually manufactured by conducting dry amthere exists an optimum'set of conditions for moniagas into molten sodium or by dissolving producing a maximum yield of. gasoline of good sodium in liquid ammonia. Other methods less anti-knock value, the use of more severe condicommonly used consist in treating sodium'oxide' 3o tions, while they may produce gasoline boiling with ammonia or by treating'sodium hydride with range fractions closely approximating a" mixture ammonia. Amides strictly analogous-to that of of aromatic hydrocarbonsin compositiomprosodium have. been prepared from each of the I ducing not only excessive gas losses but a very other metalsof'the alkali, group that'is, potasmaterial lowering in yield oi gasoline.so that-in slum, lithium; rubidium andlcaesium by the same 35 this respect it may be stated that the production general methods. but none are of great commerof increased yields of anti-knock gasoline by the cial importance .on account of the higher cost of cracking process is limited by economic conthe base materials and in thatthey offer no, de-. siderations. 7 cided advantages overthe sodium compound in 40 The present invention has as one of its objects most instances. The sodium compound melts at 40 provisionof a process by which the economic dis; approximately 310 and boils at 750 F. It advantages of producing high anti-knock value will be evident from it's constitution that. it progasoline by cracking may be oiiset by the provides a powerful reagent for use intmany chemduction concurrently in the cracking process of ical processes, particularly those in .which a recompounds having a specially high anti-knock ducing 'action 'i's required or when it is necessary 45 value so that the product of the operation contointroduce sodium into the sphere of reaction. sidered as a whole is of the high quality desired Several alternative methods of operation are and the necessary yields are maintained. possibleand are comprised within the scope of v In one specific embodiment the invention'c'omthe invention. As a generalrule, the conditions prises treating cracked hydrocarbon vapors with under which the general reactions are brought so halogenated or sulionated hydrocarbons and sodabout correspond to those of cracked vapors amide for the production ofamines to increase undergoing fractionation .un'der super-atmosthe anti-knock value of the gasoline and other pheric pressure following the, reaction zone of a treating eilects. g cracking process,.these,. conditions involvingtem- I r The types of hydrocarbon derivatives which it peratures of from approximately 300 to 600"! ll 4 and pressures in the approximate range of 100 to 400 pounds per square inch. According. to one method of operation the vapors entering a primary fractionator or separator may receive increments respectively of chlorinated or sulphonated hydrocarbons and at approximately the same point the proper amount of'sodamide, the,

subsequent fractionation serving to remove the sodium salts produced incidentally to the main reaction as a fused or soluble mass in the bottom of the fractionator or separator, and the production of amines which distill over with the gasoline fractions and add to their-anti-knock value.

Another possible method of operation which may, however, require more precautions as to shown by the following table in which the effect on anti-knock value is measured by the percentage increasein the "H. U. C. R. (highest usefulcompression ratio). It will be observed that the greatest effect is produced by methyl anilineand xylidine though their eflects areonly-siightly above that of aniline as the simplest member of the series and which would result from the interaction of chlorbenzoi and sodamide Percentage increase of H. U. C. R.

quired for interaction with the hydrocarbon derivative employed. It has at times a very pronounced desulphurizing action on account of the great afiinity of the sodium for sulphur in such compounds as mercaptans, sulphur others, etc., and may result in substantial sulphur reduction in the finished product depending upon the types of sulphur compounds present in the -cracked vapors and other conditions of operation as well as the excess of sodamide used.

The rocess of the invention may be used as 'a.single treatment on cracked vapors or in combination with preceding or succeeding treatments for producing as an overall result a finished product of desired characteristics. For example, the vapors may betreated by special desulphurizing and/or polymerizing steps prior to the introduction of the reactants for the production of amines and still further vapor phase treatments, suitable settling periods or filtering by inert or absorbent" terials may follow. In the majority of instances a final rectification to produce an end point gasoline ispreierable. Furthermore, the condensed product may require a light final washing to remove traces of reaction products.

As an example of a treatment which may be conducted. according to the process of the invention and the results obtainable therefrom, the cracked vapors of approximate gasoline boiling point range coming from the fractionator of a. cracking process operating on Mid-Continent residuum may be considered; Such vapors may be eyolved from the fractionator under a pressure of approximately 20 pounds'per square wiui No.1 petrol obtained by addition 0! an volume oi oommonorganicsubetanoes selected with reierenoetosolnbility and boiling point Chemical Melt Boilin Critical point Eifect on iormula point e point e o. n. U. o n.

Anillm OHIN -O 184 43: dry 21. 7 Moth lanilin CrHrN -'-57 194 432-442 i222 Ethy CsHnN 63 204 6-416 +10. Dl-methyl aniline- CIHIIN +2 195 420-400 +1. 7

Di-Oth l aniline- CilHisN 38 216 411-390 0 Benz anili CllHllN +33 310 Deeom 470 +9. I! Told dine. C'rHeN --21 200 1 +18. 8 xylldine (M)- ClHiiN +49 215 448 +22. 8

It is contemplated to use mixtm-es of hydrocarbon derivatives which areadaptable to-use in the process, for example, light coal tar distillates may be chlorinated and introduced into the cracking vapors along with sodamide as already de'scribedwithout resorting to the usually tedious methods of separation or individual hydrocarbons by fractionation.

a The particular hydrocarbon derivative or mix'-' ture of such employed in the process and the amount used will depend upon a varif ty offactors such as the cost ofthe compound or mixture, the character of the cracked products (which in turn depends upon the character of .the charging stock and the conditions of operation) and the knock rating desired in the finished gasoline. Chlorbenzol is ofgeneral application, as the aniline which results from it by reaction with sodamide has a high eiiect on the-anti- Y knock value of a given gasoline, this being only slightly exceeded by such compounds as cumidine, xylidine, moncmethyianiline, toluidine, etc., as shown byv he table.

In addition to the production of amin s which add to theanti-knock value of the gasoline, other treating effects may be produced by the use of sodamide if this is used in excess over that reinch and a temperature of 500 F. Chlorbenzol may-be injected into these vapors at the rateof about 12 pounds per barrel of final distillate along with approximately-4% pounds of sodamide, the vapors then passing to setting and filtering equipment to remove sludge mixtures and salts produced by the reaction. The gasoline produced by fractionating and contacting these vapors with solid absorbent materials without the use of'chlorbenzol and sodamide upon the vapors according to the process of the invention may have the properties shown in the "untreated column following, while gasoline produced by applying the process of the invention may have the properties shown in the treated" column.

Untreated Treated Octane number 66, 82 Color, Bayhol 11 N Gum content by copper dish 275 25 mp. Sulphur conten 0.2! 0.06 Color stability or loss in Saybolt degrees in the 4-hour sunlight test H The yield of gasoline in both cases may be approximately 60% of the residuum processed, with the maximum cracking temperature onployed 930 1". with a pressure of 250 pounds per square inch. To produce the 82 octane numbers by straight cracking and fractionation without es of the invention and the example of' the results obtainable by .one operation thereof is suflicient to enable one skilled in the art to recognize its value, but since theexact type of f operation may be considerably varied and the amounts of reagents alsovaried in the treatment of different stocks, the process as disclosed is not to be construed in any way as a limitation upon the broad scope of the invention.

We claim as our invention:

1. The method of improving the overhead product of a distillatory gasoline-producing 'system, which comprises introducing a sulphonating agent to a vapor zone of said system to form a sulphonated hydrocarbon derivative, contactingthe vapors containing said derivative with sodamide, and condensing the thus treated vapors.

2. The method of improving the overhead product of a distillatory gasoline-producing system, which comprises introducing a sulphonated hydrocarbonderivative to a vapor zone of said system, contacting the lvapors containing said derivative with sodamide, and condensing the thug treated vapors.

3. "Ina process for improving the anti-knock characteristics of the overhead distillate product 5 resulting from the conversion 'of. higher boiling hydrocarbons into relativelyv lower boiling hydro.- carbons by the cracking process the improvement which comprises introducing into the vapor ,zone of the said cracking process a sulphonatlng agent to produce a sulphonated hydrocarbon derivative, and thereafter subjecting the mixture of hydrocarbons and the aforementioned derivative to contact with sodamide ami condensing the thus treated vapors. 1

4. In a process for improving the antiknock characteristics of the overhead distillate product resulting from the conversion of higher boiling hydrocarbons into relatively lower boiling hydrocarbons by the cracking processfthe improvement which comprises introducing into the vapor zone. of the said cracking process a sul-- phonated hydrocarbon derivative and thereafter subjecting the mixture of hydrocarbons and the aforementioned derivative to contact'with sodamide, and condensing the thus treated vapors. JACQUE C. MORRELL. GUSTAWEGLOFF. 

